EP0484119B1 - Organopolysiloxanes and methods of making - Google Patents

Organopolysiloxanes and methods of making Download PDF

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Publication number
EP0484119B1
EP0484119B1 EP91310002A EP91310002A EP0484119B1 EP 0484119 B1 EP0484119 B1 EP 0484119B1 EP 91310002 A EP91310002 A EP 91310002A EP 91310002 A EP91310002 A EP 91310002A EP 0484119 B1 EP0484119 B1 EP 0484119B1
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European Patent Office
Prior art keywords
iii
allyl
formula
unsaturated compound
groups
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EP91310002A
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German (de)
English (en)
French (fr)
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EP0484119A1 (en
Inventor
Mitsuhiro Takarada
Yuji Yoshikawa
Kenichi Isobe
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • This invention relates to organopolysiloxanes and methods for preparing the same. More particularly, it relates to novel organopolysiloxanes having organic functional groups suitable for use as modifiers of organic resins in paint, molding material, medical material, and coating material applications.
  • organopolysiloxanes having an organic functional group were widely used as resin modifiers in the fields of paint, molding materials, medical materials, and coating materials for the purpose of imparting useful properties such as heat resistance, weather resistance, mold release, formability and thermal impact to organic resins.
  • organopolysiloxanes having an organic functional group for example, dimethylpolysiloxane having an alcoholic hydroxyl group at either end (see Japanese Patent Publication No. 8718/1979), dimethylpolysiloxane having a functional group at either end (see Japanese Patent Application Kokai Nos. 217515/1983 and 123502/1984), methylpolysiloxane having a functional group on a side chain (see Japanese Patent Publication Nos. 18960/1986 and 28880/1985), and methylphenylpolysiloxane having an alcoholic hydroxyl group at either end and on a side chain.
  • EP-A-468305 (in Article 54(3) EPC relation to the present disclosure) describes organopolysiloxanes having methyl side groups and, to give optimal adhesive release properties, a combination of epoxy-containing side groups (which may be 3-glycidoxypropyl or 2-(3',4'-epoxycyclohexyl) -ethyl groups) with R3OH side groups in which R3 is a C3 ⁇ 11 alkylene group. 3-hydroxypropyl is exemplified for the latter.
  • EP-A-281718 describes novel processes for introducing 3-acryloxypropyl or 3-methacryloxypropyl ester groups onto a silicone chain.
  • a complete or partial transesterification is proposed in which a group YOH (which may be 3-hydroxypropyl) is reacted with a lower alkyl (meth)acryloxy in the presence of a catalyst.
  • Some 3-hydroxypropyl may be left unreacted, or reacted with another side-group-forming reagent.
  • Proposed uses for the resulting organopolysiloxane oils are as an additive for silicone elastomers, and as UV-curable silicone coating compositions.
  • US-A-4294974 describes homo-and co-polymers of siloxanes carrying hydroxymethyl and/or 3-hydroxypropyl groups together with unsaturated groups which may be methacryloxypropyl. Sufficient hydroxy groups are present to give hydrophilic properties enabling use to make contact lenses.
  • organopolysiloxanes having the same functional groups in their molecule possess properties corresponding to the respective functional groups.
  • organopolysiloxane which is more compatible with organic resins and more effective as a resin modifier than the conventional organopolysiloxanes.
  • organohydrogenpolysiloxane of the following average composition formula (3): wherein R is an alkyl group having 1 to 6 carbon atoms or phenyl group, and letters a, b and c are positive numbers within the range: 1 ⁇ a ⁇ 20, 1 ⁇ b ⁇ 10, and 1 ⁇ c ⁇ 10, more particularly, by adding b mol of a first unsaturated compound to SiH of an organoorganohydrogenpolysiloxaneof formula (3) and adding c mol of a second unsaturated compound to c mol of unreacted SiH of the organohydrogenpolysiloxane of formula (3), there is obtained an organopoly
  • an unsaturated compound selected from the group consisting of allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, allyl glycol, allyl acrylate, and allyl methacrylate to SiH of an organohydrogenpolysiloxane of the following average composition formula (4): wherein Y, R, a and b are as defined above, the unsaturated compound forming a functional group different from Y of the organohydrogenpolysiloxane of formula (4), there is obtained an organopolysiloxane of the following average composition formula (2) : wherein X, Y, R, a, and b are as defined above.
  • the organopolysiloxanes of formulae (1) and (2) each having two different functional groups within a molecule are highly compatible with organic resins such as epoxy resins and acrylic resins and capable of imparting desired properties such as heat resistance, weather resistance, formability, water repellency and adhesion to the resins depending on particular types of functional groups they possess.
  • organic resins such as epoxy resins and acrylic resins
  • desired properties such as heat resistance, weather resistance, formability, water repellency and adhesion to the resins depending on particular types of functional groups they possess.
  • polysiloxanes having both epoxy and alcoholic hydroxyl groups or both (meth)acryloxy and alcoholic hydroxyl groups are effective for modifying various organic resins through grafting, thereby improving interfacial adhesion and increasing strength by utilizing a multiplicity of available crosslinking points.
  • the present organopolysiloxanes each having two different functional groups which are different in reactivity can be used in such a manner that two different modes of crosslinking occur or polymerization and crosslinking occur separately, they are advantageous resin modifiers.
  • the organopolysiloxanes of formula (2) wherein Y is 3-acryloxypropyl or 3-methacryloxypropyl group are particularly useful in that when they are subject to radical polymerization at their acryl or methacryl group or radical copolymerization at their acryl or methacryl group with other polymerizable monomers, there are obtained functional group-containing siloxane grafted acrylic polymers which were difficult to synthesize in the prior art.
  • the present organopolysiloxanes when having diphenylsiloxane or methylphenylsiloxane units incorporated therein, become more compatible with organic resins.
  • the present invention provides organopolysiloxanes of formulae (1) and (2) as defined above. Methods for producing them are by consecutive hydrosilylation of a compound of formula (3) with two different unsaturated compounds and by hydrosilylation of a compound of formula (4) with an unsaturated compound.
  • Figs. 1 to 4 are IR absorption spectra of organopolysiloxanes of the present invention.
  • the present invention provides organopolysiloxanes of the following average composition formulae (1) and (2).
  • X and Y are organic groups selected from different ones of (i), (ii) and (iii) as follows:
  • R is an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl and propyl groups or a phenyl group, with the methyl and phenyl groups being preferred for commercial purposes.
  • methyl and phenyl groups are used together.
  • a diphenylsiloxane or methylphenylsiloxane unit into a siloxane having a dimethylsiloxane unit in the backbone, there can be obtained an organopolysiloxane which is further improved in reactivity and compatibility with organic resins.
  • Letters a, b, and c are within the above-defined range. As the siloxane chain becomes longer (a, b, and c in excess of their upper limit), the siloxane becomes higher in viscosity, more difficult to handle, and less compatible with organic resins.
  • the compounds of formula (1) can be readily synthesized in high yields by incorporating different organic groups X and Y through partial hydrosilylation reaction in accordance with the following method.
  • X, Y, R, a, b, and c are as defined above.
  • the compound of formula (3') can be separately prepared by hydrolysis or equilibration reaction.
  • the organohydrogenpolysiloxane of formula (3) can be readily prepared by effecting equilibration reaction among tetramethylcyclotetrasiloxane, a cyclic polysiloxane, and a disiloxane as a terminal group in the presence of sulfuric acid or a sulfonic acid.
  • organohydrogenpolysiloxane of formula (3) are given below. In the following description, Me is methyl and Ph is phenyl.
  • the above - mentioned consecutive hydrosilylation reactions are carried out in the presence of a platinum catalyst. That is, an organohydrogenpoly-siloxane of formula (3) is partially hydrosilylated with a functional groupcontaining alkene or unsaturated compound in the presence of a platinum catalyst. After the consumption of the functional group-containing alkene is complete, hydrosilylation with another functional group-containing alkene is started.
  • platinum catalysts for hydrosilylation may be used.
  • chloroplatinic acid is preferred in that addition reaction can be complete by heating at a temperature of about 60°C to 120°C for about 2 to 8 hours.
  • the platinum catalyst is used in a catalytic amount, often about 2 to 400 ppm based on the weight of the organohydrogenpolysiloxane.
  • Reaction may be carried out in suitable solvents, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene and aliphatic hydrocarbon solvents such as hexane, heptane, and octane for controlling the reaction system viscosity and reaction temperature.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • aliphatic hydrocarbon solvents such as hexane, heptane, and octane
  • alcoholic solvents such as ethanol, isopropyl alcohol, butanol, and isobutanol may be used to which system potassium acetate is added in an amount of about 0.001 to 0.5% by weight based on the organohydrogenpolysiloxane to complete the addition reaction quickly.
  • an organopolysiloxane of formula (1) is produced by separately preparing an organohydrogenpolysiloxane of formula (3 ⁇ ) through acid equilibration reaction or decomposition reaction and effecting similar addition reaction.
  • X in formula (3′) is preferably 3-acryloxypropyl or 3-methacryloxypropyl group.
  • an organopolysiloxane of formula (2) having a terminal functional group different from a side functional group can be readily synthesized in high yields by effecting hydrosilylation reaction between a double hydrogen - terminated organopolysiloxane of average composition formula (4) and a functional group-containing alkene.
  • X, Y, R, a, b, and c are as defined above.
  • an organohydrogenpolysiloxane of average composition formula (4) is added an unsaturated compound selected from the group consisting of allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, allyl glycol, allyl acrylate, and allyl methacrylate which provides a functional group different from Y of the organohydrogenpolysiloxane of formula (4).
  • an organopolysiloxane of formula (2) is obtained by reacting of allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, allyl glycol, allyl acrylate, and allyl methacrylate which provides a functional group different from Y of the organohydrogenpolysiloxane of formula (4).
  • the functional group Y of the organohydrogenpolysiloxane of formula (4) should preferably be an organic group less reactive to sulfuric acid and sulfonic acids, typically acryloxypropyl and methacryloxypropyl groups.
  • the organohydrogenpolysiloxane of formula (4) can be readily prepared by effecting equilibration reaction among a tetraalkyldisiloxane, a hydrolysate of a dialkoxysilane containing a functional group Y, and a cyclic polysiloxane in the presence of sulfuric acid or a sulfonic acid.
  • organohydrogenpolysiloxane of formula (4) are given below.
  • Y ⁇ is a 3-acryloxypropyl or 3-methacryloxypropyl group.
  • hydrosilylation reaction between an organohydrogenpolysiloxane of formula (4) and a functional group-containing alkene may be carried out as in the above-mentioned hydrosilylation reaction to produce an organopolysiloxane of formula (1).
  • organopolysiloxanes having different functional groups in a molecule which are highly compatible with organic resins and, when added to organic resins as a silicone resin modifier, can impart to the resins heat resistance, weather resistance, formability, water repellency, adhesion or any other desired properties attributable to the functional groups.
  • the manufacturing methods of the present invention permit for easy synthesis of such organopolysiloxanes having different functional groups in high yields.
  • Example 3 The procedure of Example 3 was repeated except that 22.0 grams of allyl glycidyl ether was used instead of 19.7 grams of allyl glycol, isolating 119.8 grams (yield 99%) of a corresponding addition product which was identified to have the following average composition formula.
  • FIG. 4 Infrared absorption spectrum: FIG. 4

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)
EP91310002A 1990-10-31 1991-10-30 Organopolysiloxanes and methods of making Expired - Lifetime EP0484119B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP294962/90 1990-10-31
JP2294962A JP2751622B2 (ja) 1990-10-31 1990-10-31 オルガノポリシロキサン及びその製造方法

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EP0484119A1 EP0484119A1 (en) 1992-05-06
EP0484119B1 true EP0484119B1 (en) 1996-01-03

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EP (1) EP0484119B1 (ja)
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DE (1) DE69116092T2 (ja)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW216432B (ja) * 1992-01-10 1993-11-21 Shinetsu Chem Ind Co
US5332797A (en) * 1992-04-01 1994-07-26 Minnesota Mining And Manufacturing Company Silicone release compositions
JP2773547B2 (ja) * 1992-05-08 1998-07-09 信越化学工業株式会社 オルガノポリシロキサン及びその製造方法
EP0620242B1 (en) * 1993-04-15 1998-08-19 Dow Corning Toray Silicone Company, Limited Epoxy group-containing silicone resin and compositions based thereon
FR2707655B1 (fr) * 1993-07-02 1995-09-15 Rhone Poulenc Chimie Nouveaux polymères siliconés à fonctions oléfiniques, leur procédé de préparation et compositions durcissables comprenant lesdits polymères.
US5795947A (en) * 1993-07-02 1998-08-18 Rhone-Poulenc Chimie Olefinically functional polyorganosiloxanes and curable silicone compositions comprised thereof
JPH08325381A (ja) * 1995-05-31 1996-12-10 Toray Dow Corning Silicone Co Ltd 有機ケイ素化合物およびその製造方法
JPH0995535A (ja) * 1995-09-29 1997-04-08 Toray Dow Corning Silicone Co Ltd ジオルガノポリシロキサンおよび布帛用処理剤
JP3287786B2 (ja) * 1997-04-18 2002-06-04 信越化学工業株式会社 硬化性シリコーン組成物
JP4491283B2 (ja) * 2004-06-10 2010-06-30 信越化学工業株式会社 反射防止膜形成用組成物を用いたパターン形成方法
JP4602842B2 (ja) * 2005-06-07 2010-12-22 東京応化工業株式会社 反射防止膜形成用組成物、それを用いた反射防止膜
WO2007121513A1 (en) 2006-04-20 2007-11-01 Aortech Biomaterials Pty Ltd Gels
US20070298349A1 (en) * 2006-06-22 2007-12-27 Ruzhi Zhang Antireflective Coating Compositions Comprising Siloxane Polymer
JP6198571B2 (ja) 2012-11-30 2017-09-20 キヤノン株式会社 電子写真感光体、電子写真感光体の製造方法、プロセスカートリッジ、及び電子写真装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468305A2 (de) * 1990-07-25 1992-01-29 Th. Goldschmidt AG Härtbare Epoxygruppen aufweisende Organopolysiloxane, Verfahren zu ihrer Herstellung und ihre Verwendung als härtbare Beschichtungsmittel mit abhäsiven Eigenschaften

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294974A (en) * 1979-01-31 1981-10-13 American Optical Corporation Hydrophilic silicone compounds and contact lenses containing polymers thereof
US4293678A (en) * 1979-11-26 1981-10-06 Union Carbide Corporation Radiation-curable acrylated epoxy silicone compositions
US4576999A (en) * 1982-05-06 1986-03-18 General Electric Company Ultraviolet radiation-curable silicone release compositions with epoxy and/or acrylic functionality
US4558082A (en) * 1984-05-10 1985-12-10 General Electric Company Acrylated polymers
FR2611729B1 (fr) * 1987-02-24 1989-06-16 Rhone Poulenc Chimie Procede de preparation d'un organopolysiloxane a fonction acrylate et/ou methacrylate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468305A2 (de) * 1990-07-25 1992-01-29 Th. Goldschmidt AG Härtbare Epoxygruppen aufweisende Organopolysiloxane, Verfahren zu ihrer Herstellung und ihre Verwendung als härtbare Beschichtungsmittel mit abhäsiven Eigenschaften

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Publication number Publication date
US5248750A (en) 1993-09-28
EP0484119A1 (en) 1992-05-06
DE69116092T2 (de) 1996-07-25
JPH04168126A (ja) 1992-06-16
DE69116092D1 (de) 1996-02-15
JP2751622B2 (ja) 1998-05-18

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